CN116490568A - Polymer blends with increased temperature resistance - Google Patents
Polymer blends with increased temperature resistance Download PDFInfo
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- CN116490568A CN116490568A CN202180075935.4A CN202180075935A CN116490568A CN 116490568 A CN116490568 A CN 116490568A CN 202180075935 A CN202180075935 A CN 202180075935A CN 116490568 A CN116490568 A CN 116490568A
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- polymer composition
- blend
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- 229920002959 polymer blend Polymers 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 claims abstract description 142
- 229920000642 polymer Polymers 0.000 claims abstract description 131
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000005977 Ethylene Substances 0.000 claims abstract description 25
- 229920000098 polyolefin Polymers 0.000 claims abstract description 24
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000010512 thermal transition Effects 0.000 claims abstract description 12
- 150000008064 anhydrides Chemical group 0.000 claims abstract description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 5
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 4
- 229920000554 ionomer Polymers 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 13
- 229920001903 high density polyethylene Polymers 0.000 claims description 12
- 239000004700 high-density polyethylene Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000000518 rheometry Methods 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011734 sodium Chemical class 0.000 claims description 5
- 238000002076 thermal analysis method Methods 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052708 sodium Chemical class 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical class C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011777 magnesium Chemical class 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical class [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 22
- 238000006386 neutralization reaction Methods 0.000 description 21
- 229920001577 copolymer Polymers 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 11
- -1 polyethylene Polymers 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 229920000573 polyethylene Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 7
- 229920000092 linear low density polyethylene Polymers 0.000 description 7
- 239000004707 linear low-density polyethylene Substances 0.000 description 7
- 229920001684 low density polyethylene Polymers 0.000 description 7
- 239000004702 low-density polyethylene Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 150000003751 zinc Chemical class 0.000 description 6
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920001179 medium density polyethylene Polymers 0.000 description 4
- 239000004701 medium-density polyethylene Substances 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 102100021792 Gamma-sarcoglycan Human genes 0.000 description 2
- 101000616435 Homo sapiens Gamma-sarcoglycan Proteins 0.000 description 2
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 2
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- NKHAVTQWNUWKEO-NSCUHMNNSA-N monomethyl fumarate Chemical compound COC(=O)\C=C\C(O)=O NKHAVTQWNUWKEO-NSCUHMNNSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 125000004436 sodium atom Chemical group 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920003298 Nucrel® Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229920010346 Very Low Density Polyethylene (VLDPE) Polymers 0.000 description 1
- 238000000333 X-ray scattering Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 150000003819 basic metal compounds Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001941 electron spectroscopy Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 102000051759 human factor J Human genes 0.000 description 1
- 108700008420 human factor J Proteins 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003534 oscillatory effect Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005638 polyethylene monopolymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003938 response to stress Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003190 viscoelastic substance Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
- C08L23/0876—Neutralised polymers, i.e. ionomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Embodiments of the polymer blend may include a first polymer composition and a second polymer composition. The first polymer composition may comprise a polyolefin having a thermal transition temperature of at least 100 ℃ and a graftable monomer having at least one acid or anhydride functional group grafted onto the polyolefin. The second polymer composition may comprise an E/X/Y ethylene interpolymer, wherein E is an ethylene monomer and comprises greater than 50 weight percent of the interpolymer, and X is an alpha, beta-unsaturated C 3 ‑C 8 Carboxylic acid and comprises more than 0 to 25 wt% of the interpolymer, and Y is a polymer comprising acrylic acid C 1 ‑C 8 An optional comonomer of the alkyl ester.
Description
Technical Field
The present description relates generally to polymer blends comprising acid copolymers, ionomers, and combinations thereof, and in particular to polymer blends having enhanced temperature resistance.
Background
Polymer blends comprising acid copolymers and/or ionomers are materials commonly used in a variety of applications because they have desirable mechanical properties (e.g., notched izod impact strength), optical properties, or abrasion resistance. For example, these blends can be used in extruded articles such as films, foams, and molded articles. However, these polymer blends may have useful use temperatures below 100 ℃, making them unsuitable for certain applications where temperatures of 100 ℃ or higher may be approached in use. Thus, there is a continuing need for polymer blends with increased temperature resistance and desirable impact strength.
Disclosure of Invention
Embodiments of the present disclosure address this need for polymer blends with increased temperature resistance and desirable impact strength.
According to one embodiment, the polymer blend may include a first polymer composition and a second polymer composition. The first polymer component may comprise a polymer having a thermal transition temperature (defined as a storage modulus at 10rad/s below that measured using Dynamic Mechanical Thermal Analysis (DMTA) of at least 100 DEG C>A temperature of 10 MPa) and a graftable monomer comprising at least one acid or anhydride functional group grafted onto the polyolefin. The second polymer composition may include an E/X/Y ethylene interpolymer, wherein E is an ethylene monomer and comprises greater than 50 weight percent (wt.%) of the interpolymer, and X is an alpha, beta-unsaturated C 3 -C 8 Carboxylic acids and take up each otherMore than 0 to 25% by weight of the polymer and Y is a polymer comprising acrylic acid C 1 -C 8 An optional comonomer of the alkyl ester.
According to another embodiment, the ionomer composition may comprise a polymer blend in which the first polymer composition, the second polymer composition, or both are at least partially neutralized with a metal salt.
According to yet another embodiment, a method of preparing an ionomer composition may include blending a first polymer composition and a second polymer composition and neutralizing the first polymer composition and the second polymer composition. The first polymer composition, the second polymer composition, or both may be neutralized with a metal salt before or after blending.
Additional features and advantages will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments described herein, including the detailed description and the claims which follow.
It is to be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter.
Detailed Description
Specific embodiments of the present application will now be described. This disclosure may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth in this disclosure. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.
Definition of the definition
The term "polymer" refers to a polymeric compound prepared by polymerizing monomers (whether of the same or different types). Thus, the generic term polymer encompasses the term "homopolymer" which is generally used to refer to polymers prepared from only one type of monomer, as well as "copolymer" which refers to polymers prepared from two or more different monomers. As used herein, the term "interpolymer" refers to a polymer prepared by the polymerization of at least two different types of monomers. Thus, the generic term interpolymer includes copolymers, and polymers prepared from more than two different types of monomers, such as terpolymers.
As used herein, "polyolefin" means a polymer made up of one or more compounds having formula C n H 2n Any polymer made from olefins. Some ethylene-based polymers or propylene-based polymers as defined below may be polyolefins; however, ethylene-based polymers and propylene-based polymers encompass copolymerization with polar comonomers.
"polyethylene" or "ethylene-based polymer" shall mean a polymer comprising greater than 50 weight percent of units derived from ethylene monomers. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more comonomers). The comonomer may include an olefin comonomer and a polar comonomer. Common forms of polyethylene known in the art include Low Density Polyethylene (LDPE); linear Low Density Polyethylene (LLDPE); ultra Low Density Polyethylene (ULDPE); very Low Density Polyethylene (VLDPE); a single-site catalyzed linear low density polyethylene comprising both a linear low density resin and a substantially linear low density resin (m-LLDPE); medium Density Polyethylene (MDPE); and High Density Polyethylene (HDPE).
The term "LDPE" may also be referred to as "high pressure ethylene polymer" or "highly branched polyethylene" and is defined to mean that the polymer is partially or fully homo-or co-polymerized in an autoclave or tubular reactor at a pressure above 14,500psi (100 MPa) by using a free radical initiator such as a peroxide (see, e.g., U.S. Pat. No. 4,599,392, which is incorporated herein by reference). LDPE resins typically have a density in the range of 0.916 grams per cubic centimeter (g/cc) to 0.935 g/cc.
The term "LLDPE" includes resins prepared using Ziegler-Natta (Ziegler-Natta) catalyst systems, as well as resins prepared using single site catalysts, including but not limited to dual metallocene catalysts (sometimes referred to as "m-LLDPE") and constrained geometry catalysts; and resins prepared using post-metallocene and molecular catalysts. LLDPE comprises a linear, substantially linear or heterogeneous polyethylene copolymer or homopolymer. LLDPE comprises less long chain branching than LDPE and comprises a substantially linear ethylene polymer, further defined in U.S. Pat. No. 5,272,236, U.S. Pat. No. 5,278,272, U.S. Pat. No. 5,582,923 and U.S. Pat. No. 5,733,155; homogeneously branched linear ethylene polymer compositions, such as those in U.S. Pat. No. 3,645,992; heterophasic branched ethylene polymers, such as those prepared according to the process disclosed in U.S. Pat. No. 4,076,698; and/or blends thereof (such as those disclosed in US 3,914,342 or US 5,854,045). The LLDPE resin can be prepared via gas phase, solution phase or slurry polymerization or any combination thereof using any type of reactor or reactor configuration known in the art.
The term "MDPE" refers to polyethylene having a density of 0.926 to 0.940 g/cc. "MDPE" is typically prepared using chromium or Ziegler-Natta catalysts or using single site catalysts (including but not limited to dual metallocene catalysts and constrained geometry catalysts).
The term "HDPE" refers to polyethylene having a density greater than about 0.940g/cc, which is typically produced with Ziegler-Natta, chromium or single site catalysts, including but not limited to dual metallocene catalysts and constrained geometry catalysts.
As used herein, the term "propylene-based polymer" or "polypropylene" refers to a polymer comprising polymerized form, which refers to a polymer comprising more than 50% by weight of units that have been derived from propylene monomers. This includes propylene homopolymers, random copolymer polypropylene, impact copolymer polypropylene, propylene/alpha-olefin interpolymers, and propylene/alpha-olefin copolymers. The comonomer may include an olefin comonomer and a polar comonomer.
As used in this disclosure, the term "blend" or "polymer blend" as used refers to a mixture of two or more polymers. The blend may be miscible or may be immiscible (not phase separated at the molecular level). The blend may or may not be phase separated. The blend may or may not contain one or more domain configurations, as determined by transmission electron spectroscopy, light scattering, x-ray scattering, and other methods known in the art. Blends may be prepared by physically mixing two or more polymers at a macroscopic level (e.g., melt blending resins or compounding) or at a microscopic level (e.g., simultaneous formation in the same reactor). The blend may be prepared in the melt phase or using solution blending in a common solvent.
As used in this disclosure, the term "ionomer" refers to a polymer that includes both electrically neutral repeat units and repeat units that are covalently bonded to the polymer backbone as part of an ionized unit of pendant moieties.
As used herein, "graftable monomer" refers to a molecule that is attached (e.g., chemically bonded) to a polymer as a side chain, but does not polymerize or copolymerize as part of the polymer backbone.
The terms "comprises," comprising, "" includes, "and" including, "have" and their derivatives are not intended to exclude the presence of any additional component, step or procedure, whether or not the component, step or procedure is specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all compositions claimed through use of the term "comprising" may include any additional additive, adjuvant or compound, whether in polymeric form or otherwise. In contrast, the term "consisting essentially of excludes any other component, step, or procedure from any subsequently recited range, except for those components, steps, or procedures that are not essential to operability. The term "consisting of" excludes any ingredient, step or procedure not specifically recited or listed.
The polymer blend of the present disclosure may include a first polymer and a second polymer. It is contemplated that the polymer blends of the present disclosure can include any number of additional polymers, such as a third polymer, a fourth polymer, a fifth polymer, or a sixth polymer. Those of skill in the art will appreciate that the polymer blends of the present disclosure may be prepared using any conventional or yet to be developed method or technique.
The first polymer composition of the polymer blend of the present disclosure may include a polyolefin having a thermal transition temperature of at least 100 ℃. As used in this disclosure, thermal transition temperature may be defined as a temperature below the temperature at which the storage modulus measured using Dynamic Mechanical Thermal Analysis (DMTA) is >10MPa at 10 rad/s. In some embodiments, the polyolefin may have a thermal transition temperature of at least 105 ℃, such as at least 110 ℃, at least 115 ℃, at least 120 ℃, or at least 125 ℃.
As previously mentioned, the polyolefin of the first polymer composition of the polymer blend of the present disclosure may comprise an ethylene-based polymer or a propylene-based polymer.
In embodiments in which the polyolefin of the first polymer composition of the polymer blend of the present disclosure may comprise an ethylene-based polymer, the ethylene-based polymer may comprise a High Density Polyethylene (HDPE). In one or more embodiments, the HDPE can have a density of 0.940g/cc to 0.980g/cc, or 0.945g/cc to 0.965g/cc, or 0.945g/cc to 0.955 g/cc. In alternative embodiments, the ethylene-based polymer may comprise a Linear Low Density Polyethylene (LLDPE) or a Low Density Polyethylene (LDPE).
The polyolefin of the first polymer composition of the polymer blend of the present disclosure may have a melt index (I) of from 0.5g/10min to 300g/10min 2 ). For example, the polyolefin of the first polymer composition of the polymer blend of the present disclosure may have the following melt index (I 2 ): 0.5g/10min to 275g/10min, such as 0.5g/10min to 250g/10min, 0.5g/10min to 225g/10min, 0.5g/10min to 200g/10min, 0.5g/10min to 175g/10min, such as 0.5g/10min to 150g/10min, 0.5g/10min to 125g/10min, 0.5g/10min to 100g/10min, 0.5g/10min to 75g/10min, such as 0.5g/10min to 50g/10min, 0.5g/10min to 25g/10min, 0.5g/10min to 10g/10min, 2.5g/10min to 300g/10min, 2.5g/10min to 275g/10min, such as 2.5g/10min to 250g/10min, 2.5g/10min to 225g/10min, 2.5g/10min to 200g/10min, 2.5g/10min to 175g/10min, such as 2.5g/10min to 150g/10min, 2.5g/10min to 125g/10min, 2.5g/10min to 100g/10min, 2.5g/10min to 75g/10min, such as 2.5g/10min to 50g/10min, 2.5g/10min to 25g/10min, 2.5g/10min to 10g/10min. PolymerizationThe polyolefin of the first polymer composition of the blend may have the following melt index (I 2 ): 0.5g/10min to 60g/10min, 0.5g/10min to 50g/10min, 0.5g/10min to 40g/10min, 0.5g/10min to 30g/10min, 0.5g/10min to 20g/10min, 0.5g/10min to 10g/10min, 1.0g/10min to 60g/10min, 1.0g/10min to 50g/10min, 1.0g/10min to 40g/10min, 1.0g/10min to 30g/10min, 1.0g/10min to 20g/10min, 1.0g/10min to 10g/10min, 1.5g/10min to 60g/10min, 1.5g/10min to 50g/10min, 1.5g/10min to 40g/10min, 1.5g/10min to 30g/10min, 1.5g/10min to 10min, 1.10 min to 20g/10min or 1.5g/10 min.
The first polymer composition of the polymer blend of the present disclosure comprises a graftable monomer grafted onto a polyolefin, the graftable monomer comprising at least one acid or anhydride functional group. Of particular interest are graftable monomers having both ethylenically unsaturated groups and acid or anhydride groups. The graftable monomer may be grafted onto the polyolefin using a free radical initiator that generates free radicals. The graft polymerization reaction may be carried out in the presence of a radical generator such as an organic peroxide (e.g., an alkyl peroxide) or an azo compound. Ultrasound or ultraviolet radiation or by any high energy radiation may be used to generate free radicals. Alternatively or additionally, the graftable monomer may be grafted onto the polyolefin using thermal grafting. Thermal grafting may refer to grafting accomplished using shear and heat using an extruder or high shear mixer. The grafting level of the graftable monomer may be from 0.1 wt% to 20 wt% of the combined weight of polyolefin and graftable monomer. In embodiments, the grafting level of the graftable monomer may be 0.3 wt% to 10 wt% or 0.5 wt% to 8 wt%. In addition, the graft polymerization process may also employ coagents that aid in grafting the polyolefin and graftable monomer. Various coagents having a high level of unsaturation are considered suitable, such as allyl, vinyl, or acrylate coagents.
The graftable monomer may include acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic acid, fumaric acid, monoesters of the dicarboxylic acids, such as methyl hydrogen maleate, methyl hydrogen fumarate, ethyl hydrogen fumarate, maleic anhydride, or combinations thereof. In particular embodiments, the graftable monomer may include acrylic acid or methacrylic acid. In embodiments, the graftable monomer may comprise, consist of, or consist essentially of at least one of acrylic acid, methacrylic acid, or both grafted onto the polyolefin.
The second polymer composition of the polymer blend of the present disclosure may include an E/X/Y ethylene interpolymer. "E" of the E/X/Y ethylene interpolymer may be ethylene monomer. The ethylene monomer may comprise greater than 50% by weight of the interpolymer. "X" of the E/X/Y ethylene interpolymer may be an alpha, beta-unsaturated C 3 -C 8 Carboxylic acids. Alpha, beta-unsaturated C 3 -C 8 The carboxylic acid may comprise greater than 0 to 25 wt% of the ethylene interpolymer or 1 wt% to 10 wt% of the ethylene interpolymer. Examples of "X" may include acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic acid, fumaric acid, monoesters of said dicarboxylic acids, such as methyl hydrogen maleate, methyl hydrogen fumarate, ethyl hydrogen fumarate and maleic anhydride. In particular embodiments, "X" includes acrylic acid or methacrylic acid.
"Y" of the E/X/Y ethylene interpolymer may be a polymer comprising acrylic acid C 1 -C 8 An optional comonomer of the alkyl ester. These may include, but are not limited to, ethyl acrylate, methyl acrylate, n-butyl acrylate, isobutyl acrylate, or combinations of these.
The second polymer composition of the polymer blend of the present disclosure may have a density of 0.910g/cc to 0.990g/cc, or 0.920g/cc to 0.980g/cc, or 0.925g/cc to 0.975 g/cc.
The second polymer composition of the polymer blend of the present disclosure may have a melt index (I) of from 0.5g/10min to 500g/10min 2 ). For example, the second polymer composition of the polymer blends of the present disclosure can have the following melt index (I 2 ): 0.5g/10min to 475g/10min, such as 0.5g/10min to 450g/10min, 0.5g/10min to 425g/10min, 0.5g/10min to 400g/10min, 0.5g/10min to 375g/10min, such as 0.5g/10min to 350g/10min, 0.5g/10min to 325g/10min, 0.5g/10min to 300g/10min, 0.5g/10min to 275g/10min, such as 0.5g/10min to 250g/10min, 0.5g/10min to 225g/10min, 0.5g/10min to 200g/10min0.5g/10min to 175g/10min, such as 0.5g/10min to 150g/10min, 0.5g/10min to 125g/10min, 0.5g/10min to 100g/10min, 0.5g/10min to 75g/10min, such as 0.5g/10min to 50g/10min, 0.5g/10min to 25g/10min, 0.5g/10min to 10g/10min, 2.5g/10min to 450g/10min, 2.5g/10min to 425g/10min, 2.5g/10min to 400g/10min, 2.5g/10min to 375g/10min, such as 2.5g/10min to 350g/10min, 2.5g/10min to 325g/10min, 2.5g/10min to 300g/10min, 2.5g/10min to 275g/10min, such as 2.5g/10min to 250g/10min, 2.5g/10min to 225g/10min, 2.5g/10min to 200g/10min, 2.5g/10min to 175g/10min, such as 2.5g/10min to 150g/10min, 2.5g/10min to 125g/10min, 2.5g/10min to 100g/10min, 2.5g/10min to 75g/10min, such as 2.5g/10min to 50g/10min, 2.5g/10min to 25g/10min, 2.5g/10min to 10min. The second polymer composition of the polymer blend may have the following melt index (I 2 ): 0.5g/10min to 50g/10min, 0.5g/10min to 40g/10min, 0.5g/10min to 30g/10min, 0.5g/10min to 20g/10min, 0.5g/10min to 10g/10min, 1.0g/10min to 60g/10min, 1.0g/10min to 50g/10min, 1.0g/10min to 40g/10min, 1.0g/10min to 30g/10min, 1.0g/10min to 20g/10min, 1.0g/10min to 10g/10min, 1.5g/10min to 50g/10min, 1.5g/10min to 40g/10min, 1.5g/10min to 30g/10min, 1.5g/10min to 20g/10min or 1.5g/10min to 10min.
The polymer blends of the present disclosure may include a first polymer composition to a second polymer composition in a weight ratio ranging from 20/80 wt% to 80/20 wt%. For example, the polymer blends of the present disclosure may include a first polymer composition to a second polymer composition in a weight ratio ranging from 25/75 wt% to 75/25 wt%, such as from 30/70 wt% to 70/30 wt%, from 35/65 wt% to 65/35 wt%, from 40/60 wt% to 60/40 wt%, or from 45/55 wt% to 55/45 wt%.
The polymer blends of the present invention may also be formed into ionomer compositions. In such embodiments, the first polymer composition, the second polymer composition, or both polymers in the blend are at least partially neutralized with a metal salt that serves as the ion source. Typical ion sources include sodium hydroxide, sodium carbonate, sodium acetate, zinc oxide, zinc acetate, magnesium hydroxide, and lithium hydroxide. Other ion sources are well known and will be appreciated by those skilled in the art. In addition to sodium, zinc, magnesium and lithium ions, other alkali or alkaline earth cations are also useful and may include potassium, calcium, tin, lead, aluminum and barium. Combinations of ions may also be used. It is contemplated that the first polymer composition, the second polymer composition, or both polymers in the blend may be at least partially neutralized with a metal salt with or without a catalyst. A catalyst such as water or acetic acid may be used. The polymer blend in the ionomer composition may have any of the features or compositions as previously described in the present disclosure with respect to the polymer blend.
The degree of neutralization expected may depend on the desired application. As used in this disclosure, "degree of neutralization" may refer to the amount of acid sites neutralized by the metal salt. The degree of neutralization may be based on the amount of acid sites on the first polymer composition, the second polymer composition, or both. In embodiments, the degree of neutralization of the first polymer composition, the second polymer composition, or both may be from 15% to 90%. That is, 15% to 90% of the acid sites of the first polymer composition, the second polymer composition, or both, may be neutralized by the metal salt.
In embodiments, 15% to 90% of the acid sites of the first polymer composition, the second polymer composition, or both, can be neutralized by a metal salt, e.g., 15% to 80%, 15% to 70%, 15% to 60%, 15% to 50%, 15% to 40%, 15% to 30%, 15% to 20%, 25% to 90%, 25% to 80%, 25% to 70%, 25% to 60%, 25% to 50%, 25% to 40%, 25% to 30%, 35% to 90%, 35% to 80%, 35% to 70%, 35% to 60%, 35% to 50%, 35% to 40%, 45% to 90%, 45% to 80%, 45% to 70%, 45% to 60%, 45% to 50%, 55% to 90%, 55% to 80%, 55% to 70%, 55% to 60%, 65% to 90%, 65% to 80%, 65% to 70%, 75% to 90%, 75% to 80%, or 85% to 90%.
The ionomer compositions of the present disclosure may be defined by a rheology ratio greater than 10.0. As used in the present disclosure,"rheology ratio" may mean a ratio of 0.1s -1 And viscosity measured at 190℃and at 100s -1 And the ratio of viscosities measured at 190 ℃. In embodiments, the ionomer composition may have a rheology ratio of greater than 10.5, for example greater than 11.0, greater than 11.5, greater than 12.0, greater than 12.5, greater than 13.0, greater than 13.5, greater than 14.0, greater than 14.5, or greater than 15.0. Without being bound by theory, a rheology ratio greater than 10.0 correlates to improved processability of the polymer and/or polymer blend.
The ionomer compositions of the present disclosure may have a phase angle of less than 57 ° measured using dynamic rheology measurements (e.g., oscillatory shear measurements) at 190 ℃ and complex modulus g=20 kPa. As used in this disclosure, the "phase angle" is a measure of the stress and strain relationship that is a function of the degree to which the ionomer composition responds to a hysteresis in the strain input. For newtonian liquids, the phase angle will be 90 degrees, while for hooke's solids, the phase angle will be 0 degrees. The phase angle of the viscoelastic material (i.e., the polymer, polymer blend, ionomer, or ionomer composition of the present disclosure) falls between these two extremes. In embodiments, the ionomer composition may have a phase angle of less than 56 °, such as less than 55 °, less than 54 °, less than 53 °, less than 52 °, less than 51 °, or less than 50 °. Also, without being bound by theory, phase angles less than 57 ° are associated with improved processability of the polymer and/or polymer blend.
The polymer blends and ionomer compositions of the present disclosure may have a thermal transition temperature measured using Dynamic Mechanical Thermal Analysis (DMTA) of greater than 90 ℃, such as greater than 92 ℃, greater than 94 ℃, greater than 96 ℃, greater than 98 ℃, greater than 100 ℃, greater than 102 ℃, greater than 104 ℃, greater than 106 ℃, greater than 108 ℃, or greater than 110 ℃, which is explained in detail in the test methods section of the present disclosure.
The polymer blends and ionomer compositions of the present disclosure may additionally include minor amounts of additives including plasticizers, stabilizers (including viscosity stabilizers, hydrolysis stabilizers), primary and secondary antioxidants, ultraviolet light absorbers, antistatic agents, dyes, pigments or other colorants, inorganic fillers, flame retardants, lubricants, reinforcing agents (such as glass fibers and glass flakes), synthetic (e.g., aramid) fibers or pulp, foaming or blowing agents, processing aids, slip additives, antiblocking agents (such as silica or talc), mold release agents, tackifying resins, or combinations of two or more thereof. Inorganic fillers such as calcium carbonate may also be incorporated into the polymer blend and ionomer compositions.
These additives may be present in the polymer blend and ionomer composition in an amount ranging from 0.01 wt% to 40 wt%, from 0.01 wt% to 25 wt%, from 0.01 wt% to 15 wt%, from 0.01 wt% to 10 wt%, or from 0.01 to 5 wt%. The incorporation of the additives may be carried out by any known method, for example by dry blending, by extruding a mixture of the various ingredients, by conventional masterbatch techniques, etc.
The method of making the polymer blends of the present disclosure can include blending a first polymer composition and a second polymer composition. Similarly, the method of making the present disclosure is an ionomer composition can include blending a first polymer composition and a second polymer composition and neutralizing the first polymer composition and the second polymer composition. When neutralizing the first polymer composition and the second polymer composition, the first polymer composition, the second polymer composition, or both may be neutralized with a metal salt before or after blending.
The process of preparing the polymer blends or ionomer compositions of the present disclosure, i.e., blending and neutralization steps, can be performed in a continuous process. In embodiments where the blending and neutralization steps are performed in a continuous process, the components may be blended and neutralized using an extruder or kneader. Some examples of continuous equipment that may be used include co-rotating or counter-rotating twin screw extruders, single screw extruders, continuous mixers, reciprocating kneaders, and multi-screw extruders. The process of preparing the polymer blends or ionomer compositions of the present disclosure may alternatively be performed in a batch process. In embodiments in which the blending and neutralization steps are performed in a batch process, a batch mixer may be used to blend and neutralize the components. Some examples of batch mixers are twin roll mills, intermeshing or non-intermeshing internal mixers.
According to various embodiments, the polymer blends or ionomer compositions of the present disclosure may be used to form extruded articles, such as blown or cast films, foams, or molded articles. For example, in embodiments where a polymer blend or ionomer composition may be used to form a foam, the polymer blend or ionomer composition may be combined with additives for controlling foam properties to form foams of various shapes. In some embodiments, the foam may be extruded, for example, from a twin screw extruder, as known to one of ordinary skill in the art.
Test method
Density of
Samples for density measurement were prepared according to ASTM D1928. The polymer samples were pressed for three minutes at 190℃and 30,000psi, then for one minute at 21℃and 207 MPa. Measurements were made within one hour of sample compression using ASTM D792, method B.
2 Melt index (I)
Melt index or I 2 (g/10 min or dg/min) according to ASTM D1238, condition 190 ℃/2.16kg, procedure B.
Dynamic Mechanical Spectrum (DMS)
Under nitrogen purge, small angle (amplitude) oscillation shear measurements were performed using a TA instrument ARES equipped with 25mm parallel plates. Experiment at 190℃for 0.1s -1 To 100s -1 Is performed within a frequency range of (a). The strain amplitude was adjusted to 1% to 3% based on the response of the sample. The stress response is analyzed from the amplitude and phase, whereby the storage modulus (G'), loss modulus (G "), complex modulus (G), dynamic viscosity η, and phase angle (6) are calculated as a function of frequency. Used at 0.1s -1 And 100s -1 The ratio of shear viscosity at the shear rate of (2) is calculated as the rheology ratio. Phase angle 6 at complex modulus G of 20kPa is also recorded. Rheology ratio and 6 were used as a measure of melt elasticity and melt strength. The samples were dried overnight at 70-80 ℃ prior to testing.
Dynamic Mechanical Thermal Analysis (DMTA)
DMTA measurements were performed on ARES-G2 instruments under nitrogen purge. Samples of about 3mm thickness were die cut into rectangular specimens of 12.7mm by 30mm dimensions. Temperature scans were performed in torsion mode from 30 ℃ to 140 ℃ in 5 ℃ increments. A frequency of 10rad/s is used. The strain amplitude (0.1% to 5%) was adjusted to control the torque response. The storage modulus is measured as a function of temperature, and the temperature at which the storage modulus (G') drops below 10MPa is used as a measure of temperature resistance and is referred to as the thermal transition temperature. The samples were dried at 70-80 ℃ for 8 to 10 hours prior to testing.
Neutralization level
The% neutralization level is calculated based on the moles of neutralizing agent used in the formulation relative to the moles of acid present (grafted or partially base acid copolymer) and also illustrating the valence of the ion.
The percent neutralization of the ionomer resin can be readily calculated based on stoichiometry. For example, the ratio of the combined alkali metal cations in mole percent to the combined acid moieties of the acid copolymer in mole percent is the percent neutralization. Terms such as neutralization percentage may be used interchangeably with terms such as neutralization percentage and neutralization degree. There may be a plurality of acid moiety types in the polymer or polymer blend and a plurality of cation types for neutralizing the acid moiety. Thus, the formula for neutralization can be expressed as:
in the above formula,% NA J Is the weight percent of neutralizing agent J, MW J Is the molecular weight of the neutralizer J,% ACID a Is the weight percent of acid copolymer or graft a, and MW a Is the molecular weight of the acid type. The molecular weight of acrylic acid was 72.06g/mol, the molecular weight of methacrylic acid was 86.09g/mol, the molecular weight of zinc oxide was 81.41g/mol, and the molecular weight of sodium carbonate was 105.99. Sigma symbols represent different ion species and divisions in a moleculeThe sum of the different acid species in the mother. Factor J is the product of the valence of the ion in the molecular formula of neutralizing agent J and the atomic number. For example, in zinc oxide (ZnO), each zinc atom has a divalent state, and one zinc atom exists in ZnO. Thus, the factor ZnO is 2. For example, in sodium carbonate (Na 2 CO 3 ) In (2) each sodium atom has a valence of one and is represented by Na 2 CO 3 Two sodium atoms are present. Thus, the factor Na2CO3 is also 2.
The amount of basic metal compound that is capable of achieving the target neutralization of the acid moiety groups in the acid copolymer can be determined by adding a stoichiometric amount of basic compound calculated to neutralize the target amount of acid moieties in the acid copolymer.
Notched Izod impact Strength
Notched Izod impact strength was performed on samples cut from injection molded plaques according to ASTM D256. The test was performed at three different temperatures: 23 ℃,0 ℃ and-23 ℃.
Example
Embodiments are further illustrated by the following examples.
The following examples were prepared using various components. Table 1 lists the trade names of these components and the properties of these components. The materials used, their properties and their suppliers are summarized in the following table. Preparation of zinc oxide (ZnO) and sodium carbonate (Na) 2 CO 3 ) A masterbatch, and which is in pellet form to allow for ease of handling and feeding in subsequent steps.
TABLE 1 example Components and Properties
1 Technical data from manufacturerWatch (watch)
2 At 190℃under 2.16kg
3 77HSA grade from U.S. Zinc
4 Anhydrous sodium acetate grade from north american brinza grid (Brenntag North America)
Comparative example 1 Polymer blend
In comparative example 1, a polymer blend comprising HDPE without grafted monomer was prepared. Table 2 provides the compositions of these comparative polymer blends and their resulting properties.
The components of the examples of table 2 were mixed in a twin screw extruder. Specifically, polymers, polymer blends, ionomers, and ionomer blends were prepared on a Coperion ZSK 26 co-rotating Twin Screw Extruder (TSE) at a 60L/D ratio. The motor was rated at 40 horsepower and the maximum screw speed was 1200RPM. The feed rate was 8lbs/h and the screw speed used was 250rpm. The barrel temperature was maintained at 180℃to 200 ℃. In some experiments, deionized water was injected using a high pressure piston pump. A vacuum of 20 inches of mercury was drawn after mixing and before the die to remove by-products (water) during neutralization. The compounded material was extruded through a two hole die into a 10 foot long cooling water bath. The strands were then passed through an air knife to remove excess water and cut into pellets using a strand cutter.
The compounded pellets were injection molded into boards. Specifically, a 4 '. Times.6 '. Times.0.125 ' plate was formed using a Toyo Si-90 injection molding machine. All materials were dried at 70 ℃ for 4 hours before molding. Barrel temperatures of 170℃to 210℃were used. An injection size of 125mm, an injection speed of 75mm/s and a plasticizing screw speed of 75-100rpm were used. Injection molded plaques were used to cut specimens for DMS and DMTA testing.
As shown, the blends of table 2 with DMDA 8007 (HDPE without grafted monomer) achieved thermal transition DMTA temperatures above 100 ℃, but did not achieve rheology ratios above 10 and also did not achieve phase angles less than 57 °, a property indicating improved processability.
TABLE 2 Polymer blendsComposition and Properties
Example 2-ionomer composition with enhanced temperature resistance neutralized with zinc salt
In example 2, other blends were prepared using the same method as comparative example 1. Contrary to example 1, the first polymer compositions of the polymer blends are grafted with a graftable monomer comprising at least one acid or anhydride functional group and then at least partially neutralized using a zinc salt. Table 3 provides the compositions of various ionomer blends neutralized using zinc salts and their resulting properties. Those skilled in the art will appreciate that these ionomer blends are not ionomers in the art until they are neutralized.
Table 3 also specifies whether each example or comparative example was prepared using a one-step or two-step process. This corresponds to the above discussion of whether the first polymer composition and the second polymer composition are neutralized together or separately. In a one-step preparation process, the first polymer composition and the second polymer composition are first blended together and then neutralized. In a two-step preparation process, the first and second polymer compositions are first neutralized, then blended together and then neutralized once blended.
TABLE 3 ionomer compositions and properties using zinc salts
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1 Example 2F is an equal portion of the blend of comparative example 2B and comparative example 2C. In ex.2f, comparative example 2B and comparative example 2C were prepared (and neutralized) prior to blending together. The values in table 3 correspond to the final composition of example 2F.
2 Comparative example 2E is a blend of equal parts of comparative example 2B and DMDA 8007. Comparative example 2E was prepared in the same manner as example 2F (neutralization of the components prior to blending).
Table 3 lists various embodiments of ionomer compositions having enhanced temperature resistance. Examples 2A-2F provide embodiments of ionomer blends comprising AA grafted HDPE (Polybond 1009) and NUCREL (TM) acid copolymer or both at least partially neutralized with zinc salt. As shown in Table 3, the degree of neutralization of examples 2A-2F varied between 29.0% and 50.2%. Examples 2A-2F each have enhanced heat resistance because each example is characterized by a thermal transition DMTA temperature greater than 90 ℃. In addition, examples 2A-2F each had a rheology ratio greater than 10.0 and a phase angle less than 57. In contrast, comparative examples 2A-2E, which do not include both AA grafted HDPE and acid copolymer, fail to achieve this combination of temperature resistance and rheology ratio and phase angle.
Example 3-ionomer composition with enhanced temperature resistance neutralized with sodium salt
In example 3, the ionomer composition was prepared using the same method as in example 2. In example 3, as compared with example 2, neutralization was performed using sodium salt instead of zinc salt. Table 4 provides the compositions of the various ionomer compositions neutralized with sodium salts and their resulting properties.
Similar to table 3, table 4 also specifies whether the examples or comparative examples were prepared using a one-step or two-step process.
TABLE 4 ionomer compositions and Properties neutralized with sodium salt
1 example 3D is an equal portion of the blend of comparative example 3A and comparative example 3C. In ex.3d, comparative example 3A and comparative example 3C were prepared (and neutralized) prior to blending together. The values in table 4 correspond to the final composition of example 3D.
Table 4 lists various embodiments of ionomer compositions having enhanced temperature resistance. As shown in Table 4, the degree of neutralization of examples 3A-3D varied between 46.3% and 49.9%. Examples 3A-3D each have enhanced heat resistance because each example is characterized by a thermal transition DMTA temperature greater than 90 ℃. In addition, examples 3A-3D each had a rheology ratio greater than 10.0 and a phase angle less than 57. In contrast, comparative examples 3A-3C did not include both an AA grafted HDPE and an acid copolymer.
Example 4-notched Izod impact Strength values from various embodiments of examples 2 and 3
Table 5 provides notched izod impact strength values for the inventive examples and comparative examples of examples 2 and 3.
TABLE 5 notched Izod impact Strength
1 NB refers to notched Izod impact strength greater than 1300J/m.
As shown in table 5, the examples in table 5 exhibited much higher notched izod impact strength than the comparative examples. Indeed, many embodiments exhibit a notched Izod impact strength of greater than 1300J/m to some extent. In contrast, the comparative examples did not exhibit notched Izod impact strength greater than 60.0. Thus, these inventive polymer blends exhibit not only increased heat resistance as shown above, but also improved impact strength.
It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Accordingly, this specification is intended to cover modifications and variations of the embodiments described herein provided that such modifications and variations fall within the scope of the appended claims and their equivalents.
Claims (15)
1. A polymer blend, the polymer blend comprising:
a first polymer composition comprising:
a polyolefin having a thermal transition temperature (defined as a temperature below the temperature at which the storage modulus measured using Dynamic Mechanical Thermal Analysis (DMTA) is >10MPa at 10 rad/s) of at least 100 ℃; and
a graftable monomer comprising at least one acid or anhydride functional group grafted onto the polyolefin,
a second polymer composition comprising an E/X/Y ethylene interpolymer, wherein E is an ethylene monomer and comprises greater than 50 weight percent of the interpolymer, and X is an alpha, beta-unsaturated C 3 -C s Carboxylic acid and comprises from greater than 0 to 25 wt% of the ethylene interpolymer, and Y is a polymer comprising acrylic acid C 1 -C 8 An optional comonomer of the alkyl ester.
2. The polymer blend of claim 1, wherein the polyolefin comprises an ethylene-based polymer or a propylene-based polymer.
3. The polymer blend of claim 2, wherein the ethylene-based polymer comprises a high density polyethylene having a density greater than 0.940 g/cc.
4. The polymer blend of any preceding claim, wherein the graftable monomer comprises at least one of acrylic acid, methacrylic acid, or both grafted onto the polyolefin.
5. The polymer blend of any preceding claim, wherein the α, β -unsaturated C 3 -C 8 Carboxylic acids include acrylic acid or methacrylic acid.
6. The polymer blend of any preceding claim, wherein the polyolefin comprises a melt index (I) of from 0.5g/10min to 60g/10min when measured according to ASTM D1238 (190 ℃/2.16 kg) 2 )。
7. The polymer blend of any preceding claim, wherein the weight ratio of the first polymer composition to the second polymer composition is from 20/80 wt% to 80/20 wt%.
8. The polymer blend of any preceding claim, wherein the first polymer composition, the second polymer composition, or both comprise acrylic acid.
9. The polymer blend of any preceding claim, wherein the polyolefin has a thermal transition temperature of at least 125 ℃.
10. An ionomer composition comprising the polymer blend of any preceding claim, wherein the first polymer composition, the second polymer composition, or both are at least partially neutralized with a metal salt.
11. The ionomer composition of claim 10, wherein 15% to 90% of acid sites of the first polymer composition, the second polymer composition, or both are neutralized by the metal salt.
12. The ionomer composition of claim 10 or 11, wherein the metal salt comprises one or more salts of zinc, magnesium, lithium, aluminum, or sodium.
13. The ionomer composition according to any one of claims 10-12, wherein the ionomer composition has a rheology ratio (at a test temperature of 190 ℃) of greater than 10.0.
14. The ionomer composition according to any one of claims 10-13, wherein the ionomer composition has a phase angle of less than 57 ° (at a test temperature of 190 ℃ and a complex modulus of 20 kPa).
15. A method of making the ionomer composition of any one of claims 10-14, the method comprising:
blending the first polymer composition and the second polymer composition; and
neutralizing the first polymer composition and the second polymer composition, wherein the first polymer composition, the second polymer composition, or both are neutralized with a metal salt before or after blending.
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| US202063118202P | 2020-11-25 | 2020-11-25 | |
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| PCT/US2021/060333 WO2022115378A1 (en) | 2020-11-25 | 2021-11-22 | Polymer blends having increased temperature resistance |
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| US4076698A (en) | 1956-03-01 | 1978-02-28 | E. I. Du Pont De Nemours And Company | Hydrocarbon interpolymer compositions |
| CA849081A (en) | 1967-03-02 | 1970-08-11 | Du Pont Of Canada Limited | PRODUCTION OF ETHYLENE/.alpha.-OLEFIN COPOLYMERS OF IMPROVED PHYSICAL PROPERTIES |
| US3914342A (en) | 1971-07-13 | 1975-10-21 | Dow Chemical Co | Ethylene polymer blend and polymerization process for preparation thereof |
| US4599392A (en) | 1983-06-13 | 1986-07-08 | The Dow Chemical Company | Interpolymers of ethylene and unsaturated carboxylic acids |
| US5272236A (en) | 1991-10-15 | 1993-12-21 | The Dow Chemical Company | Elastic substantially linear olefin polymers |
| US5582923A (en) | 1991-10-15 | 1996-12-10 | The Dow Chemical Company | Extrusion compositions having high drawdown and substantially reduced neck-in |
| US5278272A (en) | 1991-10-15 | 1994-01-11 | The Dow Chemical Company | Elastic substantialy linear olefin polymers |
| US5693488A (en) | 1994-05-12 | 1997-12-02 | The Rockefeller University | Transmembrane tyrosine phosphatase, nucleic acids encoding the same, and methods of use thereof |
| JP3258534B2 (en) | 1995-07-28 | 2002-02-18 | タイコエレクトロニクスアンプ株式会社 | Female contact |
| US6420481B2 (en) * | 2000-01-21 | 2002-07-16 | E. I. Du Pont De Nemours And Comapny | Impact modified polyamide compositions |
| US20090130355A1 (en) * | 2007-11-16 | 2009-05-21 | John Chu Chen | Articles containing bimodal ionomer compositions |
| EP3591019A1 (en) * | 2018-07-02 | 2020-01-08 | E. I. du Pont de Nemours and Company | Universal thermoplastic adhesives for multilayer films |
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